4-cyanoisothiazolesulfenamides



United States Patent "ce 5,149,107 4-CYANGISQTHZAZGLESULFENAMIDESWilliam R. Hatehard, Wilmington, Deh, assignor to E. I. du Pont Nemonrsand Company, Wilmington, Del.,

a corporation of Delaware No Drawing. Filed Apr. 30, 1962, er. No.191,310 9 Ciaims. (Ci, zen-247.2

This invention relates to new isothiazole derivatives and theirpreparation.

Compounds having the isothiazoie structure, that is, the structure (thering atoms are numbered for easier reference) have been unknown untilrecently except in the form of bicyclic compounds where the isothiazolenucleus is fused to a benzene nucleus, i.e., benzoisothiazoles. It wasonly in 1956 that isothiazoles wherein the ring carbon atoms bearmonovalent substituents were first reported by Adams and Slack(Chemistry & Industry 1956, 1232). Little is known of the chemistry ofisothiazoles. In particular, no isothiazoles having sulfenarnidosubstituents have been reported.

The new compounds made available by this invention are the4-cyanoisothiazolesulfenamides of the general formula where Y ischlorine or a sulfenamido group each of R and R is hydrogen, alkyl orcycloalkyl; and R and R attached to the same nitrogen atom can togetherform a divalent radical (RR') which is an alkylene group of 2-6 chaincarbons which bear a total of up to 2(i.e., 0-2) substituents (otherthan hydrogen) of 1-2 carbons, 3-Q-1,5-pentylene, or substituted3-Q-1,5-pentylene where the substituents, which are 1-2 alkyl groups ofl-2 carbons, are bonded to carbon, Q being a chalcogen of atomic number8-16, i.e., oxygen or sulfur. The preferred sulfenamides are thosewherein R and R taken singly are hydrogen, or alkyl or cycloalkyl of11()' carbons, e.g., alkyl of 1-10 carbons, or cycloalkyl oralkylcycloalkyl of -10 carbons, and R and R taken together are asdefined above.

The products of this invention are prepared by a process which comprisesreacting an amine reactant of the formula where R and R have thepreviously stated significance (i.e., ammonia or a primary or secondaryamine), with a 4-chloroisothiazolo[4,5,d]isothiazole of the formula moleratio of about 2:1 when Y is C1 and about 4:1

when Y is SCl.

Bidhflfi? Patented Sept. 15, 1964 The reaction mechanism is not fullyknown but, in either case, the reaction results in the opening of one ofthe isothiazole nuclei between the sulfur and nitrogen atoms withformation of a cyano group.

The preferred amine reactants are those of formula R wherein R and R areas defined above in connection with the preferred products of thisinvention.

With reference to Reaction 1 above, the indicated mole ratio (2:1) ofamine reactant to 3,4-dichloroisothiazolo- [4,5,d]isothiazole is, ofcourse, desirable for full utilization of the latter reactant which isusually the more expensive one; However, it is not critical since, onthe one hand, the reaction will also proceed, although with a decreasein yield, at a lower mole ratio, e.g., 1.5 :l; and, on the other hand,an excess of amine reactant, e.g., up to a mole ratio of 4:1 or evenhigher, even though not necessary, can be used without harmfulconsequences.

With reference to Reaction 2, it is also permissible to depart from theindicated mole ratio (4:1) of amine reactant to4-chloroisothiazolo[4,5,d]isothiazolesulfenyl chloride. Thus, an excessof amine reactant, e.g., a mole ratio of 6:1 or even higher, while notnecessary, can be used if desired. On the other hand, a mole ratio lowerthan 4:1 can be used, but when this ratio isdecreased by a significantamount, a competitive reaction takes place to some extent, whereby onlythe chlorine atom of the sulfenyl chloride group reacts with the aminereactant, the 4-chloroisothiazolo portion of the molecule remainingunaffected. The product of this competitive reaction is therefore a4-chloroisothiazolo[4,5,d]-3-isothiazolesulfenamide of the generalformula For this reason, it is generally preferred that the aminereactant be used in approximately the stoiehiometric amount required byEquation 2, e. g., in a molar ratio with respect to the sulfenylchloride of at least 3.8:1, when it is desired to obtain the4-cyanoisothiazole-3,S-bis-sulfenamide essentially free from4chloroisothiazolo [4,5,d]-3-isothiazolesulfenamide, thus avoidingsubsequent separation of the two compounds. However, this is by no meansessential since useful amounts of the first named compound are obtained,in admixture with the second named compound, even when the mole ratio issubstantially lower than 4:1. In practice, it is entirely feasible touse any mole ratio of amine reactant to sultenyl chloride higher than3:1. The mixture of reaction products obtained at the lower ratio can,if desired, be separated into its components by fractionalcrystallization since the two products diflYer in solubilities andmelting points. Such a separation is, however, unnecessary for at leastone important practical application of the products of this invention,viz., their use as rubber vulcanization accelerators, since both the4-cyanoisothiazole-3,5- bis-sulfenamides and the4-chloroisothiazolo[4,5,d]-3- isothiazolesulfenamides are very effectivefor this purpose.

The conditions under which Reactions 1 and 2 are conducted are notcritical. However, the process is conveniently conducted in an organicliquid medium which is at least a partial solvent for the reactants,e.g., which dissolves them to the extent of at least 1% by weight. Anysubstantially unreactive solvent can be used for this purpose. Solventsfree from active hydrogen, that is, hydrogen attached to elements otherthan carbon, are suitable, such as aromatic hydrocarbons orhalohydrocarbons, e.g., benzene, toluene, chlorobenzene, aliphatichalohydrocarbons, e.g., carbon tetrachloride, chloroform,tetrachloroethylene; acylic or cyclic ethers, e.g., di-n-butyl ether,1,2-dimethoxyethane, tetrahydrofuran, dioxan; lietones such as acetone,methyl ethyl ketone; low melting sulfones such as cyclictetramethylenesulfone; and the like.

The reaction is often exothermic, especially when 4-chloroisothiazole[4,5,d]-3-isothiazolesulfenyl chloride is used, inwhich case it can proceed at an external temperature as low as 20 C.,and some cooling may be desirable. Ordinary temperature in the range of15 to 25 C.

is satisfactory but, if it is desired to make the reaction proceedfaster, moderate heating can be applied. There is in general noadvantage in exceeding a temperature of about 100 C. The reaction israpid and is generally substantially completed in periods varying from afew minutes to a few hours. Closed vessels can be used when the aminereactant is highly volatile.

The reaction products are in general crystalline solids soluble inorganic solvents. They can be isolated from the reaction mixture in anysuitable way. A convenient procedure consists in removing the aminehydrochloride by filtration and crystallizing the product from thefiltrate, with or without previous concentration. If necessary, it canbe recrystallized from a suitable solvent.

The invention is illustrated in the following examples, which alsodescribe the preparation of the starting materials. In addition, theresults of standard tests performed on various sulfenamides of theinvention to substantiate their utility as vulcanization acceleratorsare summarized in the examples. These tests involved determination ofMooney Scorch (ASTM-Method Dl646r-59T) and stressstrain as determined byScott machine (ASTM-D412- 51T).

EXAMPLE I 3-Chloro-4-Cyano-5 -Isothiazlesulfenylmorpholine A mixture of2.11 g. (0.01 mole) of 3,4-dichloroisothiazolo[4,5,d]isothiazole, 3.48g. (0.04 mole) of morpholine and 150 ml. of tetrahydrofuran was heatedunder reflux for 5 hours and allowed to stand overnight at roomtemperature. Filtration of the cooled reaction mixture gave 1.23 g. ofmorpholine hydrochloride. Evaporation of the filtrate andcrystallization of the residue from benzene gave 2.33 g. (89% yield) of3-chloro-4-cyano-5-isothiazolesulfenylmorpholine as glistening platesthat melted at 4 8688 C. An analytical sample recrystallized fromaqueous methanol melted at 88-885" C.

Analysis.-Calcd for C H ClN OS C, 36.74; H, 3.08; N, 16.07. Found: C,36.98; H, 3.13; N, 15.85.

Ultraviolet: A in ethanol, 282 mp. (e:7680, 272 my. (s:7 840), 222 m(5:12.,050).

Infrared: 3.37, 3.42 and 3.49 ,0. (sat. CH), 4.49 a (CN), and 6.70 and7.52 (isothiazole).

The starting material in this example,3,4-dichloroisothiazolo[4,5,d]isothiazole, may be prepared bychlorination of 2,2-dicyano-l,1-disodiomercaptoethy1ene in accordancewith the equation 2NaCl A typical preparation is as follows:

A vigorous stream of chlorine gas was passed into a stirred slurry of 20g. (0.108 mole) of 2,2-dicyano-l,ldisodiomercaptoethylene in 200 ml. ofdistilled carbon tetrachloride. The mixture was quickly heated to refluxby the heat of reaction. The chlorine flow was continued for about onehour, when the heat evolution ceased. After standing overnight, thereaction mixture was filtered to separate the sodium chloride and thefiltrate was concentrated in a stream of nitrogen to give an oilycrystalline residue. The residue was a mixture consisting principally of3,5-dichloro-4-isothiazolecarbonitrile,

with a smaller amount of 3,4-dichloroisothiazolo[4,5,d]- isothiazole.The first component was separated by extraction of the mixture with warmpetroleum ether (B.P. 30-60 C.) in which it is soluble, followed byconcentration of the petroleum ether extract and steam distillation,whereby it was obtained as a white crystalline solid, M.P. 64-65 C. Theinsoluble residue from the petroleum ether extraction consisted of 2.0g. of an orange solid, M.P. l60l70 C., which, on sublimation underreduced pressure, yielded white crystals of 3,4-dichloroisothiazolo-[4,5,dlisothiazole, MP. 183-185" C.

Analysis.Calcd for C Cl- N S C, 22.77; Cl, 33.61; N, 13.38; S, 30.39.Found: C, 23.03; Cl, 33.48; N, 13.50; S, 30.46.

The 2,2-dicyano-l,l-disodiomercaptoethylene used in the abovepreparation may be prepared and isolated by the following modificationof the procedure described in US. Patent 2,533,233:

Malononitrile (66 g., 1 mole) was added slowly to a suspension of g. (2moles) of sodium hydroxide in 900 ml. of alcohol while the temperatureof the mixture was maintained below 40 C. Then carbon disulfide (76 g.,1 mole) was added dropwise with cooling over a period of 30 minutes. Theheavy, yellow slurry was stirred an additional hour at room temperatureand filtered. The yellow residue was triturated in alcohol, collected ona filter and dried in a vacuum oven at 80 C./-1 mm. for 24 hours. Therewas obtained g. (98% yield) of 2,2-dicyano-l,1-disodiomercaptoethylene.

CHz-CHg NHzCl CHE-C H2 To a solution of 4.86 g. (0.02 mole) of4-chlor0isothiazolo[4,5,d] 3-isotldazolesulfenyl chloride in 200 ml. oftetrahydrofuran at 0-5 C. was added over a 30-minute period a solutionof 6.96 g. (0.08 mole) of morpholine in ml. of tetrahydrofuran. Thereaction mixture was allowed to warm to room temperature while beingstirred for one hour. It was then filtered to remove the morpholinehydrochloride and the filtrate was evaporated under reduced pressure togive an oily'residue. Trituration of the residue with anhydrous diethylether, followed by filtration gave, as a first crop from the etherfiltrate, 4.59 g. (67% yield) of4,4-(4-cyanoisothiazole-3,5-disulfenyl)dimorpholine, M.P. 10ll03 C. Ananalytical sample was recrystallized from a mixture of cyclohexane andbenzene.

Analysis.Calcd fOI' C12H16N402S3: C, H, N, 16.27. Found: C, 42.49; H,4.47; N, 15.31.

Ultraviolet: 1 in ethanol 282 m, (e=9400), 228 m (e=12,-900), 216 m(e=l3,400).

Infrared: 3.38, 3.45 and 3.5a (sat. CH), 4.5 (CN) and 7.45,u.(isothiazole).

The starting material in this example,4-chloroisothiazolo[4,5,d]-3-isothiazolesulfenyl chloride, is preparedby chlorination of 3,S-disodiomereapto-4-isothiazolecarbonitrile inaccordance with the equation A typical preparation is as follows:

A vigorous stream of chlorine gas was passed into a stirred slurry of 10g. (0.046 mole) of dry 3,5-disodiomereapto-4-isothiazolecarbonitrile in200 ml. of distilled carbon tetrachloride while the reaction mixture wasmaintained at reflux temperature, at first by the heat of the reactionand later by the application of heat. The hot reaction mixture wasfiltered to remove the sodium chloride. On cooling the filtrate to 0 C.there was obtained 5.9 g. of a precipitate of4-chloroisothiazolo-[4,5,d]-3- isothiazolesulfenyl chloride as yellowneedles melting at 147l49 C. A second crop of 0.7 g. (total yield 59%)was obtained by concentration of the mother liquor.

Allfll)SiS.CalCd for C Cl N S Cl, 29.16; S, 39.57. Found: Cl, 28.12; S,39.10.

The 3,5-disodiomercapto-4-isothiazolecarbonitrile used in the abovepreparation can be prepared by sulfurization of2,2-dicyano-l,l-disodiomercaptoethylene in accordance with the equationS S (NC)gC=C(SNa-)a NaSC \N A typical preparation is as follows:

A mixture of 16.0 g. of 2,2-dicyano-1,1-disodiomercaptoethylene, 200 ml.of methanol and 2.9 g. of sulfur was heated under reflux for minutes andthen filtered from a little insoluble material and evaporated to drynessat reduced pressure. The residue was taken up in 100 ml. of hot 95%ethyl alcohol, and the solution was cooled and diluted with ethylacetate and ethyl ether to precipitate the tetrahydrate of3,5-disodiomercapto-4-isothiazolecarbonitrile as a crystalline solid.The product, collected in three fractions, weighed 18.9 g. after dryingin air. Drying in a vacuum oven at 80 C. and 1 mm. of mercury pressurein the presence of phosphoric anhydride gave the anhydrous3,5-disodiornercapto-4-isothiazolecarbonitrile.

Analysis.Calcd for C N S Na C; 22.02; N, 12.84; S, 44.08. Found: C,22.29; N, 12.70; S, 42.83.

6 EXAMrLE III 4,4 -(4-Cyan0is0thiaz0le-3,5-Disulfenyl)Di-(City-2,6-

Dimethylmorpholine) To a solution of 4.86 g. (0.02 mole) of4-chloroisothiazolo[4,5,d]-3-isothiazolesulfenyl chloride in 150 ml. oftetrahydrofuran was added at 2025 C. over a period of 15 minutes asolution of 9.20 g. (0.08 mole) of cis-2,6- dimethyhnorpholine in 10 ml.of tetrahydrofuran. The mixture was stirred for 2.5 hours at roomtemperature, filtered to remove the amine hydrochloride, and thefiltrate was evaporated at reduced pressure under anhydrous conditionsto give an oily residue. Trituration of the residue in methanol andfiltration gave 5.13 g. (64% yield) of4,4-(4-cyanoisothiazole-3,S-disulfenyl)di-(cis- 2,6-dimethylmorpholine),MP. 97.5102 C. An analytical sample recrystallized from petroleum ethermelted at 106-107 C.

Analysis.Calcd for C I-I N O S C, 47.98; H, 6.04. Found: C, 47.85; H,5.94.

Ultraviolet: k in ethanol 282 m (e=9570), 217 m (e=14,000).

Infrared: 3.36, 3.41 and 3.49 a (sat. CH), 4.5 ,u (conj. CN), 6.75 and7.54 (isothiazole), 7.28 a (CCH 9.25 ,u.

EXAMPLE IV 4 -Cy-zm0'is0thiaz0le-3,5 -B is (N -Cycl0hexy lsul fenamide)S s N \C To a solution of 4.86 g. (0.22 mole) of4-chloroisothiazolo[4,5,d]-3-isothiazolesulfenyl chloride in 50 ml. oftetrahydrofuran cooled to 10 C. was added over about 20 minutes asolution of 7.92 g. (0.08 mole) of cyclohexylamine in 10 ml. oftetrahydrofuran. After the addi tion was completed, the mixture wasstirred for an additional hour at 05 C. and then allowed to stand for 2hours at room temperature. Filtration and evaporation of the filtrategave an oil that solidified on standing. Trituration of this product inwarm petroleum ether and filtration gave from the filtrate 6.7 g. yield)of crude 4-cyanoisothiazole-3,5-bis(N-cyclohexylsulfenamide) that meltedat 97-104 C. After recrystallization from hexane, this product melted at108-110 C.

AIZlL )Sl S.C31Cd for C16H24N4S3I C, H, N, 15.20. Found: C, 52.56; H,6.74; N, 15.02.

Ultraviolet: 1 in ethanol 284 m (e=11,700), 235 m, (e=11,300), 217 m(E=12,200).

Infrared: 3.0 and 3.04 ,u (NH), 3.42 and 3.5 a (sat. CH), 4.5 ,u (conj.CN), 6.75 and 7.68 pa (iso'thiazole).

a, 14 9, to?

7 p 8 EXAMPLE V TABLE I4-Cyanoisothiaz0le-3,5-Bis(N-t-Butylsulfeizamide) R Amrue Reactant NGroup 151 i'll 4(CH3)3CNH2 5 ClC-CCS Cl S Ammonia NH2 Methylamine NHCH3(CH3)3CNHSC N 2(C a)a N a 1 Diethylamine". -N(U2Hs)a H g n-Hexylamiue-NH(OH2);CH1 NC-C- SN C(C s)s l IbH-OCfYIB-P -lHB %CE2g7(3gg2 To asolution of 4.8 6 g. (0.02 mole) of 4-chl0r0iSO- necy amine 2M 3thiaz0lo[4,5,d]-3-isothiazolesulfenyl chloride in 100 ml. CED-CH2 oftetrahydrofuran at 0 5 C. was added over minutes Cyclopentylamine NHCH5.84 g. (0.08 mole) of t-butylamine. The reaction mix- CHPCH ture wasstirred for 3 hours at 35 C. and then filtered. 15 Evaporation of thefiltrate at reduced pressure gave a residual oil that crystallized oncooling and trituration CH OH; with petroleum ether. Extraction of thesolid with petroleum ether and crystallization from the extract gaveDicyclohexylamine 3.67 g. (58% yield) of 4-cyanoisothiazole-3,S-bis(N-t-2 /CH2 CHQ butylsulfenamide) that melted at 7074 C. An analyt- OH OH:ical sample crystallized from petroleum ether melted at 7375 C.

Analysis.Calcd for C I-1 N 8 C, 45.53; H, 6.37; 02115 N, 17.71. Found:C, 45.53; H, 6.30; N, 17.71. CHCH2 Ultra-7101a! max, in ethanol 281 l 26 Diethy1 ;yc1oh y1g,min NH (;H CH2 '217 my. (e=l1,800). Infrared: 3.07M (NH), 3.42 ,t (sat. on 4.53 a (conj. CN), 7.6 a (isothiazole). C2115EXAMPLE VI 1,] l-Cyanoisothiaz0le-3,S-Disulfenyl)Dipiperidine s s011F011; IfiT (If H 4HN CH2 Cl-GC-C-S0l UHF-CH2 OIL-CH S H20 /l\ S (1 I/OH;OH1 CH2 CH3 CH2OH2 NOC-C-SN 0H; 20H; NHgCl CHz-Gfig CHE CH2 Asolution of 4.86 g. (0.02 mole) of 4-chloroisothi- TABLE IC011tiI111e(1azolo[4,5,d]-3-isothiazolesulfenyl chloride in 25 ml. of Rtetrahydrofuran was added dropwise to a stirred solution of 6.84 g.(0.08 mole) of piperidine in 100 ml. of tetra- Amine Reactflnt Grouphydrofuran at 1520 C. The reaction mixture was then stirred 5 hours atroom temperature, then allowed to stand overnight. Filtration removed4.55 g. (94% yield) CH G2H6 of piperidine hydrochloride. Evaporation ofthe filtrate gmhylet-h lemmine I gave a residual oil which was taken upin ether. The 59 y L ether solution was Washed successively with water,dilute CH2 hydrochloric acid and water. After drying and evapora-GET-CH2 tion of the ether, an oil remained that crystallized on standingto give 5.5 g. (80% yield) of 1,1-(4-cyanozMethylpymhdmeisothiazole-3,5-disulfenyl)dipiperidine as a yellow solid, E M.P. 69-73"C. The infrared spectrum was consistent on, with the assigned structure.

H H 11 While the lnventronhas been illustrated in the fore- C 2-0 r0 2going detailed examples by reference to certain specific Hexamethylemmmareactants and reaction products, it is, of course, not 60 CHz-CHz-CHzlimited thereto. Thus, examples of other 3-chloro- CHPCH,4-cyano-5-isothiazolesulfeuamides of the formula Thiamorphollne -NH S on/N s l:l) IR, CH? 2 R NCCCC1 Examples of other4-cyanoisothiazole-3,S-bis-sulferiwhich can be prepared by the procedureof Example I include those shown in Table I below where, for the sake ofbrevity, only the name of the amine reactant and the formula of the c B,group are given.

amides of the formula \N S G u N n 3 It Nooo-s-N which can be preparedby the procedure of Examples 11-- VI include those shown in Table IIbelow, where the head g a e the: same as in Table I.

TABLE II Amine Reaetant N Group Ammonia D irnethylamine EthylamineIsopro pylamin n-Amylamine -NH(CH2)4CH Ethyl (n-hexyDamine N\ z) a Han-Octylarm'ne NH( 011910113 Di-n-octylarnine N[(C H101 CH3]:n-Decylamine NH(CH2)QCH3 C Hr C H z Cyclopentylarnine -NHCH I 0 H2 0 HzN-E thylcyelohexylamine N GHQ-0H2 cg 011, O H:- 0 H:

C H- 0 H2 2,6-Diethyleyclohexylamina- NH-Cl 1\ /OH:

(I) H- 0 Hz C 2H5 CH2 CH2 2-Decahydronaphythylamme. NH(')H OH (3H1 C H:0g 0 H: 0 H2 C H2 C H2 Ethylemmine -N\ 0 H- 0 Ha l2,3-D1methylethy1en1rmne N\ l] C H- C H:

0 Hz- C H: Pyrrolidine -N\ I 0 Ha-- 0 Hz C H C H: 2,6-Diethy1piperidine-N\ /OH:

(1 H- C H: C 2H5 C H:- C H2- 0 H2 Hexamethylenimine -N\ C H:- 0 H2- 0 H20 Hz- 0 Hz Thiamorpholine -N S C H2 0 Hz 0 H:- H 2-Methy1thiamorpholmeN\ /S 0 Hz- 0 Hz The 4-cyanoisothiazolesulfenamides of this inventionare, as a class, highly effective as rubber vulcanization acceleratorsas illustrated by the above-mentioned tests on synthetic rubber (25/75styrene/butadiene copolymer) and on natural rubber.

Since obvious modifications and equivalents in the invention will beapparent to those skilled in the chemical arts, I propose to be boundsolely by the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound of the formula:

where Y is a member of the group consisting of chlorine and -S-N(R)R';each of R and R taken individually is a member of the group consistingof hydrogen, alkyl of 1 to 10 carbons and cycloalkyl of 5 to 10 carbons;and R and R taken together are a member of the class consisting ofalkylene of 2-6 chain carbons which bear a total of up to 2 alkylsubstituents of 1-2 carbons, 3-Q-1,5-pentylene, and substituted3-Q-l,5-pentylene where the substituents, which are 1-2 alkyl groups of1-2 carbons, are bonded to carbon, Q being a chalcogen of atomic number8-16.

2. 3-chloro-4-cyano-5-isothiazolesulfenylmorpholine.

3. 4,4-(4-cyanoisothiazole-3,S-disulfenyDdirnorpholine.

4. 4,4-(4-cyanoisothiazole-3,S-disulfenyl)di (cis 2,6-dimethylmorpholine) 5. 4 cyanoisothiazole 3,5 bis(Ncyclohexylsulfenamide).

6. 4-cyanoisothiazole-3 ,5-bis (N-t-butylsulfenamide 7.l,1'-(4-cyanoisothiazole-3,S-disulfenyl)dipiperidine.

8. A process of preparing 4-cyanoisothiazole-3,S-bis- (sulfenamides)which comprises contacting, in an organic solvent free of activehydrogen and at a temperature of up to 0., one mole of4-chloroisothiazolo[4,5,d]-3- isothiazolesulfenyl chloride with fourmoles of an amine reactant of the formula where each of R and R takenindividually is a member of the group consisting of hydrogen, alkyl of 1to 10 carbons and cycloalkyl of 5 to 10 carbons; and R and R takentogether are a member of the class consisting of alkylene of 2-6 chaincarbons which bear a total of up to 2 alkyl substituents of 1-2 carbons,3-Q-1,5-pentylene, and substituted 3-Q-l,5-pentylene were thesubstituents, which are 1-2 alkyl groups of 1-2 carbons, are bonded tocarbon, Q being a chalcogen of atomic number 8-16.

9. A process of preparing 3-halo-4-cyano-5-isothiazolesulfenamides whichcomprises contacting, in an organic solvent free of active hydrogen andat a temperature of up to 100 C., one mole of3,4-dichloroisothiazolo[4,5,d]-

isothiazole with two moles of an amine reactant of the formula whereeach of R and R taken individually is a member of the group consistingof hydrogen, alkyl of 1 to 10 carbons and cycloalkyl of 5 to 10 carbons;and R and R taken together are a member of the class consisting ofalkylene of 2-6 chain carbons which bear a total of up to 2 alkylsubstituents of 1-2 carbons, 3-Q-1,5-pentylene, and substituted3-Q-1,5-pentylene where the substituents, which are 1-2 alkyl groups of1-2 carbons, are bonded to carbon, Q being a chalcogen of atomic number8-16.

References Cited in the file of this patent UNITED STATES PATENTS2,980,679 Pala Apr. 18, 1961

1. A COMPOUND OF THE FORMULA: